Process for fluoro derivative-substituted aryl pnictogens and their oxides

ABSTRACT

A process to prepare substituted aryl pnictogen derivatives comprising contacting a fluoropolyether or fluoroalkyl primary bromide or iodide, with a pnictogen derivative such as triaryl phosphine, triaryl arsine, or triaryl stibine or triaryl phosphine oxide, triaryl arsine oxide or triaryl stibine oxide, to produce the corresponding fluoropolyether- or fluoroalkyl-substituted aryl phosphine oxide, aryl arsine oxide or aryl stibine oxide; and optionally, contacting the oxide product with a reducing agent to form the corresponding substituted aryl phosphine, arsine or stibine.

BACKGROUND OF THE INVENTION

Due to their thermal stability, perfluoropolyether fluids have a greatpotential for use as engine oils, hydraulic fluids and greases. However,a drawback in their use results from the fact that certain metals arecorroded by such fluids at temperatures of about 550° F. and above in anoxidative environment.

In U.S. Pat. No. 4,454,349, the preparation ofperfluoroalkylether-substituted phenyl phosphines, having the structureof Formula 1 below, is described:

wherein

R_(f)—O—R_(f) is a perfluoroalkyl ether group containing at least oneether linkage. Examples of R_(f)—O—R_(f) included:

C₃F₇O[CF(CF₃)CF₂O]_(x)CF(CF₃)—,

C₂F₅O(CF₂CF₂O)_(y)CF₂—, and

CF₃O(CF₂O)_(z)CF₂—,

wherein

x, y, and z are zero or an integer having a value of 1 to 20 andpreferably 1 to 4.

Such phosphine derivatives are disclosed as being corrosion andoxidation inhibitors in polyfluoroalkylether polymeric fluids inlong-term and wide temperature range applications. Temperature rangesare typically −100° F. to greater than 550° F., (−73° C. to greater than288° C.). Incorporation of these compounds in perfluoroalkylether fluidsinhibits the oxidation-corrosion of various metals with which the fluidscome into contact. These additives also prevent decomposition of suchfluids when exposed to a high-temperature oxidative environment.

The effectiveness of perfluoropolyether-substituted phosphines as 100oxidation inhibitors in perfluoropolyether fluids is well known to thoseskilled in the art and has been described and quantified in severalpatents, for instance by Snyder, et al., in U.S. Pat. Nos. 4,438,006 and4,438,007, and by Christian, et al., in U.S. Pat. Nos. 4,431,555, and4,431,556. Perfluoroalkyl substituted phosphines have been used influorous phase catalyst systems, Hope, et al., Polyhedron 18(22), 1999,pp. 2913-2917.

However, the synthesis described in U.S. Pat. No. 4,454,349 involvesmultiple steps requiring the use of hazardous and pyrophoric reactantsand reaction temperatures ranging between −80° C. and 200° C. Theprocess includes two reaction steps requiring n-butyllithium and anintermediate sulfur tetrafluoride/hydrogen fluoride fluorination step.Consequently, such potentially useful perfluoroalkylether substitutedphenyl phosphines have remained effectively inaccessible.

The mechanism of free-radical perfluoroalkylation of aromatics has beenstudied and discussed by Bravo et al., in Journal of Organic Chemistry,62(21), 1997 pp. 7128-7136. Bravo et al. studied the reaction of aperfluoroalkyl iodide (such as perfluoro-n-butyl iodide) with variousaromatic compounds, including benzene and biphenyl.

It would be desirable to improve the synthesis of the perfluoroalkyl andperfluoropolyether-substituted aryl phosphines, such as the phenylphosphines described above, and to have available the antimony andarsenic analogs. The present invention provides such a process.

SUMMARY OF THE INVENTION

The present invention provides a process to prepare a substituted arylpnictogen, and its corresponding oxide. The process comprises (a)contacting a compound selected from the group consisting offluoropolyether primary bromide, fluoropolyether primary iodide,fluoroalkyl primary bromide and fluoroalkyl primary iodide, with atriaryl phosphine, triaryl arsine, triaryl stibine, triaryl phosphineoxide, triaryl arsine oxide, or triaryl stibine oxide to produce thecorresponding mono-substituted, di-substituted, tri-substituted, or acombination of two or more thereof, fluoropolyether- orfluoroalkyl-substituted aryl phosphine oxide, aryl arsine oxide or arylstibine oxide; and optionally, (b) contacting the oxide product of step(a) with a reducing agent to form the correspondingfluoropolyether-substituted aryl phosphine, aryl arsine, or arylstibine. More specific embodiments are described hereinbelow.

DETAILED DESCRIPTION

Trademarks and trade names used herein are shown in upper case.

A common characteristic of fluoropolyethers is the presence offluoroalkyl ether moieties. Perfluoropolyether is synonymous toperfluoropolyalkylether. Other synonymous terms frequently used include“PFPE”, “PFPE oil”, “PFPE fluid”, and “PFPAE”. Another usefulfluorinated segment is a fluoroalkyl group.

The term “pnictogens” collectively indicates the elements in thePeriodic Table of Elements belonging to Group V. Herein the term“pnictogens” is constrained to indicate the subset P, As, and Sb, and“triaryl pnictogens” collectively refers to triaryl phosphines, triarylarsines and triaryl stibines. The triaryl pnictogens useful in thepractice of the first step of the present invention are compoundsdescribed below.

The process of the present invention provides syntheses of mono-, di-,and tri-substituted fluoropolyether-substituted aryl andfluoroalkyl-substituted aryl phosphine, arsine, and stibine. Forexample, these compounds may have the structure of Formula 2:[R_(f) ¹—(C_(t)R_((u+v)))]_(m)E(O)_(n)(C_(t)R¹_((u+v+1)))_((3−m))  Formula 2wherein

R_(f) ¹ is a fluoropolyether or fluoroalkyl chain. Preferably, R_(f) ¹has a formula weight ranging from about 200 to about 15,000. Preferably,R_(f) ¹ comprises repeat units. More preferably, R_(f) ¹ is selectedfrom the group consisting of:

(a) J-O—(CF(CF₃)CF₂O)_(c)(CFXO)_(d)CFZ-;

(b) J¹-O—(CF₂CF₂O)_(e)(CF₂O)_(f)CFZ¹-;

(c) J²-O—(CF(CF₃)CF₂O)_(j) CF(CF₃)CF₂—;

(d) J³-O—(CQ₂-CF₂CF₂—O)_(k)—CQ₂-CF₂—;

(e) J³-O—(CF(CF₃)CF₂O)_(g)(CF₂CF₂O)_(h)(CFXO)_(i)—CFZ-;

(f) J⁴-O—(CF₂CF₂O)_(r)CF₂—;

(g) Q(C_(p)F_(2p))—; and

(h) combinations of two or more thereof

wherein

J is a fluoroalkyl group selected from the group consisting of CF₃,C₂F₅, C₃F₇, CF₂Cl, C₂F₄Cl, C₃F₆Cl, and combinations of two or morethereof;

c and d are numbers such that the ratio of c:d ranges from about 0.01 toabout 0.5;

X is F, CF₃, or combinations thereof;

Z is F, Cl or CF₃;

J¹ is a fluoroalkyl group selected from the group consisting of CF₃,C₂F₅, C₃F₇, CF₂C₁, C₂F₄Cl, and combinations of two or more thereof;

e and f are numbers such that the ratio of e:f ranges from about 0.3 toabout 5;

Z¹ is F or Cl;

J² is C₂F₅, C₃F₇, or combinations thereof;

j is an average number such that the formula weight of R^(f) ranges fromabout 400 to about 15,000;

J³ is selected from the group consisting of CF₃, C₂F₅, C₃F₇, andcombinations of two or more thereof;

k is an average number such that the formula weight of R_(f) ranges fromabout 400 to about 15,000;

each Q is independently F, Cl, or H;

g, h and i are numbers such that (g+h) ranges from about 1 to about 50,the ratio of i:(g+h) ranges from about 0.1 to about 0.5;

J⁴ is CF₃, C₂F₅, or combinations thereof;

-   r is an average number such that the formula weight of R_(f) ranges    from about 400 to about 15,000; and

p is an integer from 4 to about 20 and C_(p)F_(2p) is a linear divalentperfluoroalkyl radical;

each R and R¹ is independently H, a C₁-C₁₀ alkyl, a halogen, OR³, OH,SO₃M, NR² ₂, R³OH, R³SO₃M, R³NR² ₂, R³NO₂, R³CN, C(O)OR³, C(O)OM,C(O)R³, or C(O)NR² ₂, or combinations of two or more thereof;

wherein

R² is independently H, C₁-C₁₀ alkyl, or combinations of two or morethereof;

R³ is a C₁-C₁₀ alkyl; and

M is hydrogen or a metal, preferably not aluminum; more preferably, M ishydrogen or an alkali metal, still more preferably, M is hydrogen,sodium or potassium;

t is equal to (6+u);

u is any combination of 0, 2, 4, 6, 8, 10, 12, 14, 16;

v is independently either 2 or 4;

n is 0 or 1;

E is P, As, or Sb, preferably E is P; and

m is greater than 0 to about 3.

The process of the present invention comprises a first step comprisingcontacting a fluoropolyether or fluoroalkyl primary bromide or iodidewith a triaryl derivative of phosphorus (triaryl phosphine or triarylphosphine oxide), arsenic (triaryl arsine or triaryl arsine oxide), orantimony (triaryl stibine or triaryl stibine oxide). Preferably afluoropolyether or fluoroalkyl primary bromide or iodide is contactedwith a triarylphosphine. Said contacting step is optionally performed inthe presence of one or more of a radical initiator, a solvent, and acatalyst, to produce a corresponding fluoropolyether-substituted aryl orfluoroalkyl-substituted aryl phosphine oxide,fluoropolyether-substituted aryl or fluoroalkyl-substituted aryl arsineoxide, or fluoropolyether-substituted aryl or fluoroalkyl-substitutedaryl stibine oxide. The process of the present invention, optionally,further comprises contacting the fluoropolyether- orfluoroalkyl-substituted aryl phosphine oxide, arsine oxide, or stibineoxide with a reducing agent to form a fluoropolyether- orfluoroalkyl-substituted aryl phosphine, arsine, or stibine.

In one particular embodiment, the pnictogen is phosphorous and afluoropolyether or fluoroalkyl primary iodide is used and there is aratio of the iodide to the triaryl phosphine of 3:1. In an alternativeto this embodiment, there is a ratio of the iodide to the triarylphosphine of 1:1. In either of these embodiments, the triaryl phosphineis preferably triphenylphosphine.

Fluoropolyether primary bromides or iodides useful in the first step ofthe present invention include, but are not limited to, those having theformulae of:F(C₃F₆O)_(z)CF(CF₃)CF₂Y;F(C₃F₆O)_(x)(CF₂O)_(w)CF₂Y;F(C₃F₆O)_(x)(C₂F₄O)_(q)(CF₂O)_(w)CF₂Y;(R_(f) ³)₂CFO(C₃F₆O)_(x)CF(CF₃)CF₂Y;F(C_(p)F_(2p))Y;and combinations of two or more thereof;wherein

Y is I or Br;

x is a number from 2 to about 100;

z is a number from about 3 to about 50, preferably from about 3 to about25, more preferably from about 3 to about 10;

q is a number from 2 to about 50;

w is a number from 2 to about 50;

p is an integer from 4 to about 20 and C_(p)F_(2p) is a linear divalentperfluoroalkyl radical;

each R_(f) ³ can be the same or different and is independently amonovalent C₁ to C₂₀ branched or linear fluoroalkane;

C₃F₆O is linear or branched.

A preferred perfluoropolyether bromide or iodide has the formulaF(C₃F₆O)_(z)CF(CF₃)CF₂Y where Y and z are defined above.

Triaryl phosphines, triaryl arsines, and triaryl stibines useful in thefirst step of the present invention include, but are not limited to,compounds having the structure of Formula 3:(C_(t)R_((u+v+1)))_(m)E(O)_(n)(C_(t)R¹ _((u+v+1)))_((3-m))  Formula 3wherein

E, R, R¹, t, u, v, m, and n are the same as defined for Formula 2,above. Preferably, E is P.

Preferred starting materials for the process of this invention are thetriaryl phosphines, arsines and stibines; more preferred are triarylphosphines, still more preferred is triphenyl phosphine or its oxide.

Suitable radical initiators for use in the first step include, but arenot limited to, peroxides such as benzoyl peroxide and t-butyl peroxide.When used, a radical initiator is preferably added in two or moreportions. The preferred initiator is benzoyl peroxide.

Suitable solvents include liquid aliphatic alcohols and carboxylicacids, preferably carboxylic acids, and more preferably, glacial aceticacid.

Suitable catalysts include any compound that promotes the formation of afluoroalkyl or fluoropolyether free radical. Cupric acetate, ferricacetate, ferric chloride, or combinations of two or more thereof areexamples of suitable catalysts. Cupric acetate is preferred. When used,the catalyst is typically present in an amount in the range of fromabout 0.0001 to about 5 weight %, based on the weight of the primarybromide or iodide compound.

The first step reaction is conducted at a temperature in the range ofabout 50° C. to about 210° C., preferably between about 70° to about110° C. The reaction product is typically washed with a suitable organicsolvent, for example, a 1:1 acetone:water mixture or glacial aceticacid, filtered, and stripped of volatile byproducts by distillationunder reduced pressure to yield the fluoropolyether- orfluoroalkyl-substituted aryl phosphine oxide, aryl arsine oxide, or arylstibine oxide.

The optional second step of the process of the present inventioncomprises contacting, in an inert solvent such as diethyl ether, thefluoropolyether- or fluoroalkyl-substituted aryl phosphine oxide, arylarsine oxide or aryl stibine oxide with a reducing agent at atemperature from about 0° C. to about 12° C., preferably about 4° C.Lithium aluminum hydride, LiAlH₄ may be conveniently used. Optionally,prior to adding the reducing agent, the oxide may be contacted with analkyl iodide such as methyl iodide, at ambient temperature, such as atabout 25° C. This step may further comprise hydrolyzing the excessreducing agent, for example, LiAlH₄, with water or dilute hydrochloricacid, (for example, 2M HCl). This step may also further comprise washingthe product with water and dilute HCl, and vacuum distilling the washedproduct. An inert fluorinated solvent is optionally used to aidtransfer. Suitable inert fluorinated solvents are1,1,2-trichlorotrifluoroethane or methyl perfluorobutyl ether (HFE-7100,available from 3M Corp., St. Paul, Minn.). This step may still furtheroptionally comprise dissolving the distilled product in the same or adifferent inert fluorinated solvent, filtering, and redistilling undervacuum, to remove volatiles to yield the product.

While not wishing to be bound by theory, it is believed that thefluoropolyether- or fluoroalkyl-substitution occurs on the arylsubstituent through a free radical mechanism similar to that describedby Bravo et al. in Journal of Organic Chemistry, 62(21), 1997, pp.7128-7136.

Compositions

The process of this invention provides some novel compositions offluoropolyether- and fluoroalkyl-substituted pnictogen derivatives. Moreparticularly, the compositions of this invention may have the structureFormula 2, as described hereinabove.

End Uses

The fluoropolyether-substituted aryl phosphines, aryl arsines, arylstibines and corresponding oxides prepared according to the presentinvention are useful as additives to perfluoropolyether oils and greasesfor lubrication purposes under extreme temperature conditions, such asin military applications. In practice, a perfluoropolyether lubricantmay comprise one or more of the fluoropolyether-substituted arylphosphines, aryl arsines, aryl stibines and the oxides thereof preparedby processes of the present invention. The fluoropolyether-substitutedaryl phosphines, aryl arsines, aryl stibines and the oxides are added tothe perfluoropolyether lubricant in an amount of about 0.1 to about 5%by weight, based on the weight of the perfluoropolyether lubricant, andpreferably from about 1 to about 2% by weight.

The fluoropolyether-substituted phosphines and fluoroalkyl-substitutedphosphines prepared according to the present invention are useful asfluorous phase catalysts in hydroformylation reactions.

Materials and Test Methods

HFE-7100, methyl perfluorobutyl ether, is available from 3M Corp., St.Paul, Minn.

KRYTOX Iodide [F(C₃F₆O)_(z)CF(CF₃)CF₂I where z has an average value ofabout 4-5] is produced by the methods described in U.S. Pat. No.6,653,511, incorporated herein by reference.

Triaryl phosphines, stibines, and their derivatives are available fromSigma-Aldrich Chemical, Milwaukee, Wis.

CELITE 521 is a diatomaceous earth filter aid available fromSigma-Aldrich Chemical, Milwaukee, Wis.

Methods for testing the corrosion and oxidation inhibiting properties ofthe perfluoropolyether-substituted aryl phosphines, arsines and stibinesprepared by the process of the present invention are as described indetail by Snyder et al. in U.S. Pat. Nos. 4,438,006 and 4,438,007, andby Christian et al. in U.S. Pat. Nos. 4,431,555, and 4,431,556. The testinvolves the immersion of steel, titanium, and other metals and alloysin formulations comprising 1% of the phosphine, arsine, or stibine, in aperfluorinated polyalkylether fluid. The metal samples are immersed inthe formulations at temperatures of about 600° F. to about 650° F.(316-343° C.) as air is bubbled through the formulation to create anoxidizing environment. For the examples tested hereinbelow (ComparativeExample and Example 3), the metal samples are immersed in 1%formulations of the Comparative Example or Example 3 in aperfluoropolyether oil. The tests are performed at 300° C. (572° F.),315° C. (599° F.), and 330° C. (626° F.). The change in the metal sampleweight per unit surface fluoropolyether-substituted aryl phosphineseffectively eliminates significant corrosion of the metal withdegradation of the lubricant observed in the absence of the additive.

The perfluoroalkylether-substituted aryl phosphine,[F(C₃F₆)OCF(CF₃)CF₂OCF(CF₃)CF₂—C₆H₄]₃P, prepared according to thesynthetic procedure described in U.S. Pat. No. 4,454,349, Example 1, isused as the Comparative Example.

EXAMPLES Example 1 Preparation of[F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₄]₃P═O

A flask is charged with F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂I (200 g, 0.16 mol,z_(avg)=4.3), glacial acetic acid (200 mL), copper(II) acetate (0.60 g,0.0032 mol), and triphenylphosphine (14.4 g, 0.0552 mol). The reactionmass is stirred and heated to 70° C., then benzoyl peroxide (38 g) isadded, and the temperature raised to 90° C. Two more additions ofbenzoyl peroxide (each 38 g) are made in 40-minute intervals, for atotal of 114 g. When GC/MS analysis indicates all the iodide is reacted,the crude product is then washed three times with 200 mL of 1:1water:acetone solution and purified by oil pump vacuum (1 mmHg, 130 Pa)distillation at 120° C. The sample is then filtered through a Büchnerfunnel with a 0.25 inch (6.4 mm) layer of CELITE 521 (see MATERIALS) ona WHATMAN #1 filter paper, yielding 138 g (71% yield). Furtherpurification by distillation at 220° C. using a molecular drag pump (0.1mmHg, 13 Pa) on 88 g of the sample to eliminate byproducts yieldspurified [F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₄]₃P═O, as evidenced by ¹H,¹⁹F, and ³¹P NMR, and semi-quantitative X-Ray Fluorescence (XRF)(P=0.750±0.038%) (44 g, 35.5%).

Example 2 Preparation of [F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₄]₃P═O

A flask is charged with F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂I (50 g, 0.042 mol,z_(avg)=4.3) and triphenylphosphine (3.91 g, 0.015 mol). The reactionmass is stirred and heated to 210° C. for 24 hours. The reaction iscomplete when GC/MS analysis indicates all the iodide is reacted. Thedesired product, [F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₄]₃P═O, is obtained,as evidenced by ¹H, ¹⁹F, and ³¹P NMR.

Example 3 Reduction of [F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₄]₃P═O

To [F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₄]₃P═O (492.75 g, 0.134 mol,z_(avg)=4.8 prepared as in Example 1) is added anhydrous diethyl ether(500 mL) at room temperature with stirring. Methyl iodide (9.16 mL,0.147 mol) is then added and the mixture stirred for 3 hours. Thereaction vessel is then cooled to 4° C. using an ice water bath, and a1M LiAlH₄ solution in diethyl ether (335 mL, 0.335 mol) is slowly addedusing an addition funnel. After stirring for 4 hours at 4° C., theexcess LiAlH₄ is hydrolyzed using 500 mL of water. The aqueous layer isdrawn off, and the mixture is then subsequently washed with 500 mL 2MHCl twice. HFE-7100 (20 mL) is then added to aid transfer to adistilling flask. The product is distilled at 120° C. with oil pumpvacuum (1 mmHg, 0.13 kPa.), yielding[F(CF(CF₃)CF₂O)_(n)CF(CF₃)CF₂—C₆H₄]₃P, as evidenced by ¹H, ¹⁹F, and ³¹PNMR, and semi-quantitative XRF (P=0.983±0.049%) (482.97 g, 98.0%).

Example 4 Preparation of [F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₄][C₆H₅]₂P═O

A flask is charged with F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂I (50 g, 43 mmol,z_(avg)=5.43), glacial acetic acid (500 mL), and triphenylphosphine(67.77 g, 280 mmol). The reaction mass is stirred and heated to 70° C.,then benzoyl peroxide (10 g) is added, and the temperature raised to 90°C. Five more additions of benzoyl peroxide (each 10 g) are made in1.5-hour intervals, for a total of 60 g. When GC/MS analysis indicatesall the iodide was reacted, the crude product is then washed three timeswith 200 mL of 1:1 water:acetone solution and purified by oil pumpvacuum (1 mmHg, 130 Pa) distillation at 120° C. The sample is thenfiltered through a CELITE 521 bed as in Example 1. Further purificationby distillation at 220° C. using a molecular drag pump (0.1 mmHg, 13 Pa)eliminates poly-HFPO byproducts, yielding purified[F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₄][C₆H₅]₂P═O, as evidenced by ¹H, ¹⁹F,and ³¹P NMR and semi-quantitative XRF (P=2.67±0.08%) (19.55 g, 30.5%).

Example 5 Reduction of [F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₄][C₆H₅]₂P═O

To [F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₄][C₆H₅]₂P═O (10.7 g, 7.2 mmol,z_(avg)=5.29 prepared as in Example 4) is added anhydrous diethyl ether(12 mL) at room temperature with stirring. Methyl iodide (0.577 mL, 9.4mmol) is then added and the mixture stirred for 2 hours. The reactionvessel is then cooled to 4° C. using an ice water bath, and a 1M LiAlH₄solution in diethyl ether (21.5 mL, 21.5 mmol) is slowly added using anaddition funnel. After stirring for 4 hours at 4° C., the excess LiAlH₄is hydrolyzed using 40 mL of water. The aqueous layer is drawn off, andthe mixture is then subsequently washed with 40 mL water, then twicewith 40-mL portions of 5% HCl. HFE-7100 (20 mL) is then added to aidtransfer to a distilling flask. The crude product is distilled at 100°C. with oil pump vacuum (1 mmHg, 130 Pa). The product is thenre-dissolved in HFE-7100 (20 mL) and filtered in a Büchner funnelthrough WHATMAN #1 filter paper to eliminate solid impurities. Theproduct is re-distilled at 115° C. with oil pump vacuum (1 mmHg, 130 Pa)for 2 h, yielding

[F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₄][C₆H₅]₂P═O, as evidenced by ¹H, ¹⁹F,and ³¹P NMR, and semi-quantitative XRF (P=3.50±0.09%) (7.44 g, 69.5%).

Example 6 Preparation of [F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₄]₃Sb═O

A flask is charged with F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂I (50 g, 42 mmol,z_(avg)=4.27), glacial acetic acid (50 mL), Copper(II) acetate (0.15 g,0.8 mmol), and triphenylantimony (4.77 g, 13.5 mmol). The reaction massis stirred and heated to 70° C., then benzoyl peroxide (5 g) is added,and the temperature raised to 90° C. Five more additions of benzoylperoxide (each 5 g) are made in 1.5-hour intervals, for a total of 30 g.When GC/MS analysis indicates all the iodide is reacted, the crudeproduct is then washed three times with 100 mL of 1:1 water:acetonesolution and purified by oil pump vacuum (1 mmHg, 130 Pa) distillationat 120° C. The sample is then filtered through a Büchner funnel with a0.25 inch (6.4 mm) layer of CELITE 521 (see MATERIALS) on a WHATMAN #1filter paper, yielding 29.1 g (64.5%). Further purification bydistillation at 220° C. using a molecular drag pump (0.1 mmHg, 13 Pa)eliminates poly-HFPO byproducts, yielding purified[F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₄]₃Sb═O, as evidenced by ¹H, ¹⁹F, and³¹P NMR, and semi-quantitative XRF (Sb═3.02±0.20%) (13.52 g, 29.9%).

Example 7 Reduction of [F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₄]₃Sb═O

To [F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₄]₃Sb═O (5.0 g, 7.2 mmol,z_(avg)=5.29 prepared as in Example 6) is added anhydrous diethyl ether(5 mL) at room temperature with stirring. Methyl iodide (0.10 mL, 1.63mmol) is then added and the mixture stirred for 3 hours. The reactionvessel is then cooled to 4° C. using an ice water bath, and a 1M LiAlH₄solution in diethyl ether (3.4 mL, 3.4 mmol) is slowly added using anaddition funnel. After stirring for 4 hours at 4° C., the excess LiAlH₄is hydrolyzed using 20 mL of water. The aqueous layer is drawn off, andthe mixture is then subsequently washed twice with 50 mL of 5% HCl.HFE-7100 (10 mL) is then added to aid transfer to a distilling flask.

The product is distilled at 115° C. with oil pump vacuum (1 mmHg, 0.13kPa), yielding [F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₄]₃Sb, as evidenced by¹H and ¹⁹F NMR, and semi-quantitative XRF (Sb=1.07±0.08%) (3.67 g,73.4%).

Example 8 Preparation of[F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₃(ortho-CH₃)]₃P═O

A flask is charged with F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂I (50 g, 42 mmol,z_(avg)=4.3), glacial acetic acid (50 mL), copper(II) acetate (0.15 g,0.8 mmol), and tri-ortho-tolylphosphine (4.10 g, 13.5 mmol). Thereaction mass is stirred and heated to 70° C., then benzoyl peroxide (5g) is added, and the temperature raised to 90° C. Two more additions ofbenzoyl peroxide (each 5 g) are made in 1.5-hour intervals, for a totalof 15 g. When GC/MS analysis indicates all the iodide is reacted, thecrude product is then washed three times with 100 mL of 1:1water:acetone solution and purified by oil pump vacuum distillation (1mmHg, 130 Pa) at 120° C. The sample is then filtered through a Büchnerfunnel with a 0.25 inch (6.4 mm) layer of CELITE 521 (see MATERIALS) ona WHATMAN #1 filter paper, yielding 19.18 g (43.1%). Furtherpurification by distillation at 220° C. using a molecular drag pump (0.1mmHg, 130 Pa) eliminates poly-HFPO byproducts, yielding purified[F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂C₆H₃(ortho-CH₃)]₃P═O, as evidenced by ¹H,¹⁹F, and ³¹P NMR, and semi-quantitative XRF (P=1.37±0.06%) (9.75 g,21.9%).

Example 9 Preparation of[F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₃(ortho-CH₃)][F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₄]₂P═O

A flask is charged with F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂I (50 g, 42 mmol,z_(avg)=4.27), glacial acetic acid (50 mL), anddiphenyl(ortho-tolyl)phosphine (3.87 g, 14 mmol). The reaction mass wasstirred and heated to 70° C., then benzoyl peroxide (5 g) was added, andthe temperature was raised to 90° C. Two more additions of benzoylperoxide (each 5 g) were made in 1.5-hour intervals, for a total of 15g. When GC/MS analysis indicated all the iodide was reacted, the crudeproduct was then washed twice with 40 mL of glacial acetic acid. Theglacial acetic acid washes were then extracted with 30 mL HFE-7100, theextracts added to the product layer, and purified by oil pump vacuum (1mmHg, 0.13 kPa) distillation at 120° C. Further purification bydistillation at 220° C. using a molecular drag pump (0.1 mmHg, 0.013kPa) was effected to eliminate poly-HFPO byproducts, yielding purified[F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₃(ortho-CH₃)][F(CF(CF₃)CF₂O)_(z)CF(CF₃)CF₂—C₆H₄]₂P═O,as evidenced by ¹H, ¹⁹F, and ³¹P NMR, and semi-quantitative XRF(P=1.36±0.06%) (21.02 g, 42.0%).

Test Results

The test results below show both Comparative Example 1 (Comp. Ex.) andthe product of the new process (Example 3) to be equivalent. In theTable, % Viscosity Change, Acid Number Change, Fluid Loss and MetalWeight Change are given as average values over a number of trials. TABLEMetal Weight Test % Viscosity Acid Number Change Product Temp. Change mgKOH/g Fluid Loss +UZ,36/41 (mg/cm²) Tested (a) ° C. @ 40° C. metal WtChange % Wt Loss 4140 Steel Comp. Ex. in 300 0.45 0.00 0.00 0.10 DEMNUMS-65 (b) Example 3 in 300 1.35 0.00 0.00 0.06 DEMNUM S-65 (b) Comp. Ex.in 315 0.55 0.00 0.00 0.43 DEMNUM S-65 (b) Example 3 in 315 1.70 0.000.52 0.08 DEMNUM S-65 (b) Comp. Ex. in 315 5.65 Not 0.00 −0.02 KRYTOX143AC (c) Determined Example 3 in 315 10.23 0.00 1.46 0.06 KRYTOX 143AC(c) Comp. Ex. in 330 3.69 0.00 0.79 1.95 KRYTOX 143AC (c) Comp. Ex. in330 3.88 0.00 0.69 1.00 KRYTOX 143AC (c) Comp. Ex. in 330 5.20 Not 0.00−1.56 KRYTOX 143AC (c) Determined Example 3 in 330 10.53 0.00 0.93 0.96KRYTOX 143AC (c) Metal Weight Change (mg/cm²) 52100 410 440C ProductBearing Stainless M50 Stainless Fluid Tested (a) Steel Steel Tool SteelSteel Appearance Comp. Ex. in 0.10 0.02 0.26 0.00 Not DEMNUM S-65 (b)Determined Example 3 in 0.04 0.02 0.05 0.01 No Change DEMNUM S-65 (b)Comp. Ex. in 0.46 0.10 0.91 0.91 Not DEMNUM S-65 (b) Determined Example3 in 0.09 0.02 0.12 0.04 No Change DEMNUM S-65 (b) Comp. Ex. in 0.070.05 0.05 0.05 No Change KRYTOX 143AC (c) Example 3 in 0.05 0.01 0.130.03 No Change KRYTOX 143AC (c) Comp. Ex. in 0.07 0.05 0.01 0.01 Hazywith metal KRYTOX 143AC (c) particles Comp. Ex. in 0.06 0.00 0.11 0.09No Change KRYTOX 143AC (c) Comp. Ex. in 0.04 −0.07 −1.93 −0.36 No ChangeKRYTOX 143AC (c) Example 3 in 0.32 0.03 0.53 0.07 No Change KRYTOX 143AC(c)(a) Each Product Tested was a formulation containing 1% of the productfrom either the Comparative Example or Example 3in the specifiedperfluoropolyether oil.(b) DEMNUM S-65 is a perfluoropolyether oil available from DaikinIndustries, Osaka, Japan.(c) KRYTOX 143AC is a perfluoropolyether oil available from E. I. duPont de Nemours and Company, Wilmington, DE.

1. A process to prepare a fluoropolyether- or fluoroalkyl-substitutedaryl pnictogen comprising contacting a compound selected from the groupconsisting of fluoropolyether primary bromide, fluoropolyether primaryiodide, fluoroalkyl primary bromide and primary fluoropolyether iodide,with a triaryl stibine or triaryl stibine oxide, to produce thecorresponding mono-substituted, di-substituted, tri-substituted, or acombination of two or more thereof, fluoropolyether- orfluoroalkyl-substituted or aryl stibine oxide.
 2. The process of claim 1further comprising contacting the oxide product with a reducing agent toform the corresponding fluoropolyether- or fluoroalkyl-substituted arylstibine.
 3. (canceled)
 4. The process of claim 3 wherein the triarylstibine is triphenylstibine.
 5. The process of claim 1 performed in thepresence of one or more of a radical initiator, a solvent and acatalyst.
 6. The process of claim 5 performed in the presence of aradical initiator and further wherein the radical initiator is aperoxide.
 7. The process of claim 6 wherein the radical initiator isbenzoyl peroxide or t-butyl peroxide.
 8. The process of claim 5performed in the presence of a solvent and further wherein the solventis a liquid aliphatic alcohol or a carboxylic acid.
 9. The process ofclaim 8 wherein the solvent is glacial acetic acid.
 10. The process ofclaim 1 performed at a temperature of about 50° C. to about 210° C. 11.The process of claim 10 is performed at a temperature of about 70° C. toabout 110° C.
 12. The process of claim 2 wherein the reducing agent islithium aluminum hydride.
 13. The process of claim 12 the reducing stepis performed at a temperature from about 0° C. to about 12° C.
 14. Theprocess of claim 13 wherein the reducing step is performed at atemperature of about 4° C.
 15. The process of claim 2 wherein, prior tothe reducing step, the oxide is contacted with an alkyl iodide.
 16. Theprocess of claim 15 wherein the alkyl iodide is methyl iodide.
 17. Theprocess of claim 1 wherein a fluoropolyether primary iodide orfluoroalkyl primary iodide is contacted with a triaryl stibine ortriaryl stibine oxide.
 18. The process of claim 17 wherein the iodidehas the formula F(C₃F₆O)_(z)CF(CF₃)CF₂Y wherein Y is I and z is 2 to 50.19. The process of claim 17 wherein the iodide has the formulaF(C_(p)F_(2p))Y wherein Y is I and p is from 4 to about
 20. 20. Theprocess of claim 18 or 19 wherein the iodide is contacted with a triarylstibine.
 21. The process of claim 20 wherein the triaryl stibine istriphenyl stibine.
 22. The process of claim 21 wherein the ratio of theiodide to the stibine is 3:1.
 23. The process of claim 21 wherein theratio of the iodide to the stibine is 1:1.